Leveling composition and method for electrodeposition of metals in microelectronics

ABSTRACT

The present disclosure relates to a leveling composition for electrodepositing metals. The composition comprises a compound of formula (I):

The present application is a continuation of U.S. patent applicationSer. No. 13/281,924, filed Jun. 24, 2014. The entirety of which ishereby incorporated by reference.

TECHNICAL FIELD

The present invention generally relates to electroplating,electroplating additives, method of electroplating, metal plating; andthe use of additives in an electrolytic deposition chemistry, and amethod for depositing metal or metal alloys; and more specifically toleveler additives for use in an electrolytic deposition chemistry, and amethod for copper metallization in printed wiring board (PWB),semiconductor integrated circuits, microelectromechanic systems (MEMS),surface mount technology (SMD), connectors, base station, light emittingdiode (LED), and molded interconnection devices (MID); and even morespecifically to leveler additives for use in an copper electrolyticdeposition chemistry for semiconductor chip interconnection.

BACKGROUND

Metallic copper is an excellent material for chip interconnection due toits advantages such as good electrical conductivity, high thermalconductivity, low melting point and extensibility. Copper plating is themethod of choice for copper interconnection. However, with continuedminimization of the chip line width, it becomes harder and harder todeposit copper metal lines without defects. A defect-free copper platingis achieved by integrating seamlessly the plating chemistry, platingtool, and semiconductor chips.

The challenges in acid copper plating have always been 1) levelingeffect, 2) said leveling effect over a wide range of aspect ratio(depth:width) preferably found on the same die, 3) achieving thedesirable leveling effect at high current densities therefore increasingthe manufacturing throughput, 4) levelers that are non-toxic,environmental friendly, 5) levelers that are easily analyzable byconventional means so their concentrations can be monitored andcontrolled in a plating bath, 6) minimizing by-products which often havedetrimental effect on bath stability. The quality of the leveler in anacid copper plating chemistry determines the quality of copper pillars,under bump metallurgy (UBM), redistribution lines (RDLs) as well as itsability to fill through silicon vias (TSVs). Most of the MEMs, LED, andsemiconductor customers require flat and smooth surfaces but there aresome applications that require convex surfaces. The selection andoptimization of electroplating conditions, especially the platingchemistry, play a key role in obtaining desired surface topographies.Many of the users of such plating chemistries are large semiconductorfabs, integrated device manufacturers (IDMs), or packaging houses whotypically process semiconductor chips with different geometries,dimensions, including different heights. The fabs and packaging housesare making these semiconductor chips for fabless companies, IDMs and/orend users. Because the design of each and every one of these companiesis different, this requires that the plating processes employed by thefabs and packaging houses are versatile and have a wide process window.For example, a fab makes semiconductor chips for fabless companies andIDMs. One of the steps is to electroplate copper pillars with viadiameters ranging from about 10 μm to about 200 μm, and the heightranging from about 20 μm to about 150 μm . If the fab could use a singlecopper plating chemistry to meet all of its customer requirements onfeature topography and within die uniformity, it would significantlyreduce its manufacturing cost. If the fab uses multiple copper platingchemistries to cover the full range of the feature dimension, it wouldincrease the manufacturing cost because it has to deal with not only anumber of different chemistries, but also associated cost for productinventory, process control and maintenance, etc. Currently, in themarket, there is no single commercial copper plating chemistry thatcould produce microchips with a wide range of feature dimensions at highyield, nor could a single commercial copper plating chemistry produceflat or convex topography by simply adjusting the concentration orcomposition. In addition, not a single commercial copper platingchemistry could produce same topography for features from about 10 um toabout 150 um at deposition rate as high as 10 A/dm²(ASD) or 5 um/min. Atypical acid copper plating chemistry includes virgin makeup solution(VMS), which includes a metal salt, an acid, and chloride ion, andorganic additives. The content of organic additives is typically verylow (at ppm level) but they determine the surface features well as bulkproperties of the electroplated layer. Organic additives can becategorized as a suppressor (or wetting agent), leveler (or grainrefiner) and accelerator (or brightener). A suppressor acts as a wettingagent which helps to wet the metal surface so plating can take place.During deposition, it suppresses the growth rate of the deposited metalso it can grow by a layer by layer mechanism. Consequently, it resultsin adhesive, smooth metal surfaces without dendrites. A copper platingbath containing only a suppressor produces a matte or dull surface. Tothis composition, one can add a leveler. By definition, it levels orfills the “potholes” of the deposited surface in such a way that theheight difference between the highest point and the lowest point of agiven feature is minimized. In addition, a good leveler also ensures theheight difference between the tallest and the shortest bump in a die isminimized. A copper plating bath contains both a suppressor and aleveler produces a surface that is somewhat reflective but not bright.To this composition, one can add an accelerator. By definition, itincreases the copper deposition rate at the deposition potential. At thesame time, it results in a reflective, shining surface. In semiconductorcopper plating, the most critical component is the leveler, becauseultimately it determines the within die uniformity, which largelydetermines the yield. Although choosing the right suppressor is alsocrucial, especially in the case of copper damascene, the core technologyinnovation today centers around the leveler for UBM, RDL, copper pillarand TSV plating. This is because taller features and larger dimensionsare required for these applications (height 3 um to 100 um, line width 2um to 20 um, diameter 10 to 100 um), therefore maintaining yieldat >99.9% becomes extremely challenging. In addition, when taller copperpillar is required, it is critical to deposit copper at high depositionrate such as 10 ASD (5 um/min) or above so high productivity can beachieved. This allows the manufacturer to reduce the unit cost thereforeto maintain its competitiveness. Clearly there is a need for versatileelectrolytic copper deposition chemistry. As described below, thepresent invention offers such a solution by employing quaternaryammonium salts of dialkylaminoalkyl esters of 10-thiaxanthenecarboxylicacid and its derivatives as levelers. Although there are commercialcopper plating baths that could meet one or more of the six challengesmentioned previously, there is none that could meet all six. Thecomposition and method of present invention could as described below.

SUMMARY

In one aspect, a leveling composition comprises a compound of formula(I):

L, X, R¹, R², R³, R⁴, Y¹, Y²,Y³,Y⁴, Y⁵, Y⁶,Y⁷, and Y⁸ are as definedbelow.

In another aspect, the compounds are of the formula (II):

X, R¹, R², R³, R⁴, is defined as below.

In yet another aspect, a method for a metal onto a substrate comprises:contacting a substrate with an electrolytic metal deposition compositioncomprising a source of metal ions, and a leveler composition, whereinthe leveler composition comprises the compound of formula (I); andapplying an electrical current to the electrolytic depositioncomposition to deposit a metal onto the substrate.

BRIEF DESCRIPTION OF THE FIGURES

FIG. 1 is a copper pillar with a flat topography.

FIG. 2 is a copper pillar with a convex topography.

FIG. 3 is a copper pillar with a concave topography.

FIG. 4 is a Hull cell panel of copper deposition at 3 A for 2 minutes inthe presence of L113.

FIG. 5 is a Hull cell panel of copper deposition at 3 A for 2 minutes inthe presence of L113 plus a suppressor, note the improvement of platingat low current density region. The panel is somewhat reflective but notbright.

FIG. 6 is a Hull cell panel of copper deposition at 3 A for 2 minutes inthe presence of L113 plus a suppressor and an accelerator, note theimprovement of plating. The entire panel becomes reflective and bright.

FIG. 7 is a Hull cell panel of copper deposition at 3 A for 2 minutes inthe presence of L26 (a typical conventional leveler) plus a suppressorand an accelerator.

FIG. 8 is the 3D laser microscope imaging of a copper pillar with L26 asthe leveler, pillar diameter=100 μm.

FIG. 9 is the 3D laser microscope imaging of a copper pillar with L113as the leveler, pillar diameter=100 μm.

FIG. 10 is the 3D laser microscope imaging of a copper pillar with L117as the leveler, pillar diameter=100 μm.

FIG. 11 is the 3D laser microscope imaging of a copper pillar with L26as the leveler, pillar diameter=80μm.

FIG. 12 is the 3D laser microscope imaging of a copper pillar with L113as the leveler, pillar diameter=80 μm.

FIG. 13 is the 3D laser microscope imaging of a copper pillar with L117as the leveler, pillar diameter=80 μm.

FIG. 14 is the 3D laser microscope imaging of a copper pillar with L26as the leveler, pillar diameter=60 μm.

FIG. 15 is the 3D laser microscope imaging of a copper pillar with L113as the leveler, pillar diameter=60 μm.

FIG. 16 is the 3D laser microscope imaging of a copper pillar with L117as the leveler, pillar diameter=60μm.

FIG. 17 is the 3D laser microscope imaging of a copper pillar with L26as the leveler, pillar diameter=40 μm.

FIG. 18 is the 3D laser microscope imaging of a copper pillar with L113as the leveler, pillar diameter=40μm.

FIG. 19 is the 3D laser microscope imaging of a copper pillar with L117as the leveler, pillar diameter=40 μm.

FIG. 20 is the 3D laser microscope imaging of a copper pillar with L26as the leveler, pillar diameter=20 μm.

FIG. 21 is the 3D laser microscope imaging of a copper pillar with L113as the leveler, pillar diameter=20 μm.

FIG. 22 is the 3D laser microscope imaging of a copper pillar with L117as the leveler, pillar diameter=20 μm.

FIG. 23 is the 3D laser microscope imaging of a copper pillar withL117+L26 as the leveler, pillar diameter=20 μm.

FIG. 24 is the 3D laser microscope imaging of a copper pillar with L26as the leveler, pillar diameter=10 μm.

FIG. 25 is the 3D laser microscope imaging of a copper pillar with L113as the leveler, pillar diameter=10 μm.

FIG. 26 is the 3D laser microscope imaging of a copper pillar with 117as the leveler, pillar diameter=20 μm.

FIG. 27 is the 3D laser microscope imaging of a copper pillar withL117+L26 as the leveler, pillar diameter=10 μm.

DETAILED DESCRIPTION OF THE DISCLOSURE

The present invention is directed to a composition and a method forelectrodepositing of metal layers. In some preferred embodiments, theinvention is directed to the composition and method for depositingcopper or copper alloys. In some embodiments, the present invention isdirected to a composition and a method for metalizing an interconnectfeature in a semiconductor circuit device substrate, i.e., a wafer ordie with desirable surface topography, good within die uniformity athigh deposition rate. The semiconductor integrated circuit devicesubstrate, i.e., a wafer or die, has a front surface and a back surface.The front surface is the surface on which integrated circuitry is built.Accordingly, the interconnect feature, i.e., a redistribution line or acopper pillar, is located on the front surface of the semiconductorsubstrate. The feature has an opening in the front surface of thesubstrate, a sidewall extending from the front surface of the substrate,and a bottom. The bottom is pre-deposited with a thin layer of copperseed layer. On a single die, features with same dimension or featureswith different dimensions can be found depending on customer design. Insome cases, different features with different dimensions are builtwithin a die. Needless to say, it is easier to realize copper depositionwith same feature and same dimension than same feature but differentdimensions on a die. During electroplating, the wafer is immersed intothe plating bath, only the front surface where there are openings isconductive. When electrical connection is made between an anode and acathode, both of which are immersed in the plating bath, electriccircuitry is complete, and copper metallization by electrodepositiontakes place. The quality of the plated surface is directly affected bythe additives that are used in the plating bath.

Semiconductor substrates may comprise large sized (40 to 150 microns),low aspect ratio (0.3 to 1.25) via features, or small sized (10 nm to 30microns), high aspect ratio (1.5 to 20) via features.

Semiconductor substrates may comprise lines with width ranging from 10nm to 20 μm, length ranging from 20 nm to 200 μm.

These features may be located in a patterned dielectric film, thedielectric film is located on a semiconductor substrate. Thesemiconductor substrate may be, for example, a semiconductor wafer orchip. The semiconductor wafer is typically a silicon wafer or siliconchip, although other semiconductor materials, such as germanium, silicongermanium, silicon carbide, silicon germanium carbide, gallium nitrideand gallium arsenide are applicable to the method of the presentinvention.

The semiconductor substrate has deposited thereon a dielectric film. Thedielectric film is typically deposited on the semiconductor wafer orchip and then patterned by lithography, to achieve the circuitry patterncomprising the aforementioned redistribution lines, trenches, and vias.

In many logic, memory, power, and Radio Frequency (RF) devices, a smoothcopper surface with flat topography is desirable. In other words, thecopper surface should be shining, and flat from one end to another. Thisis especially true when the application is radio frequency. If thesurface is rough, and/or surface topography is not flat, a percentage ofthe signal will be lost due to the so called skin effect, causingperformance issues. In the case of copper pillar, especially if thesubsequent interconnection is with another copper surface, it iscritical that both surfaces are flat, otherwise the joint formed duringthe copper-copper bonding would not be strong enough to last during theproduct warrantee period. In some cases, a surface with slight convexshape maybe desirable. In most of the cases, a concave surface isundesirable for copper-copper bonding because no bond can be formed nearthe center of the feature. This would render the joint unreliable.Therefore, for copper pillar plating, it is important that the platingchemistries shall produce plated copper surface with slightly convexprofile or preferably flat topography. As mentioned previously, theadditive in an acid copper plating bath that controls the surfacemorphology is the leveler. Conventional levelers today can largelyfulfill the role of producing slight convex surface. For some viadimensions, they can also produce flat topography. However, they arefound not to be able to produce flat topography for ALL via dimensionsAT THE SAME TIME when via diameters vary from about 10 microns to about150 microns. One embodiment of the present invention is directed to amethod of depositing bright copper pillars with flat topography withdiameters ranging from about 10 microns to about 150 microns.

The method of the present invention comprises the incorporation of oneof a particular class of leveler additives into the electrolytic copperplating chemistry. Plating chemistries containing these leveleradditives produce excellent leveling effect over a wide range of featureaspect ratios and at high current densities. One embodiment of thismethod has been found to produce copper pillars and RDLs with flattopography for the dimensions described above. In addition, theseleveler additives can produce copper pillars and RDLs with flattopography in one single bath composition. Furthermore, the copperpillars or RDLs with different sizes on a single die can be produced. Inone embodiment, incorporation of one or more of this class of leveleradditives with conventional leveler could produce copper pillar with anysurface topography at will.

Definitions

When describing the compounds, compositions, methods and processes ofthis disclosure, the following terms have the following meanings, unlessotherwise indicated.

The term “halogen” means a chlorine, bromine, iodine, or fluorine atom.

The term “alkyl” means a hydrocarbon group that may be linear, cyclic,or branched or a combination thereof having the number of carbon atomsdesignated (i.e., C₂₋₁₂ means two to twelve carbon atoms). Examples ofalkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl,t-butyl, isobutyl, sec-butyl, cyclohexyl, cyclopentyl,(cyclohexyl)methyl, cyclopropylmethyl, bicyclo[2.2.1]heptane,bicyclo[2.2.2]octane, etc. Alkyl groups can be substituted orunsubstituted, unless otherwise indicated. Examples of substituted alkylgroups include haloalkyl, thioalkyl, aminoalkyl, and the like.

The term “alkenyl” means a hydrocarbon group that contains at least onecarbon-to-carbon double bond. Alkenyl groups can include, e.g., allyl,1-butenyl, 2-hexenyl and 3-octenyl groups.

The term “alkynyl” means a hydrocarbon group that contains at least onecarbon-to-carbon triple bond. Alkynyl groups can include, e.g., ethynyl,propargyl, and 3-hexynyl. Alkenyl and alkynyl groups can be substitutedor unsubstituted, unless otherwise indicated.

The term “aryl” means a polyunsaturated, aromatic hydrocarbon grouphaving 5-10 atoms and forming a single ring (monocyclic, preferably with6 atoms such as phenyl) or multiple rings (bicyclic (preferably with 10atoms such as naphthyl) or polycyclic), which can be fused together orlinked covalently. Examples of aryl groups include phenyl andnaphthalene-1-yl, naphthalene-2-yl, biphenyl and the like. Aryl groupscan be substituted or unsubstituted, unless otherwise indicated.

The term “heteroaryl” means an aromatic group containing 5-10 atoms andat least one heteroatom (such as S, N, O, Si), where the heteroarylgroup may be monocyclic (with preferably 5 or 6 atoms) or bicyclic (withpreferably 9 or 10 atoms). Examples include pyridyl, pyridazinyl,pyrazinyl, pyrimidinyl, triazinyl, quinolinyl, quinoxalinyl,quinazolinyl, cinnolinyl, phthalazinyl, benzotriazinyl, purinyl,benzimidazolyl, benzopyrazolyl, benzotriazolyl, benzisoxazolyl,isobenzofuryl, isoindolyl, indolizinyl, benzotriazinyl, thienopyridinyl,thienopyrimidinyl, pyrazolopyrimidinyl, imidazopyridines,benzothiazolyl, benzofuranyl, benzothienyl, indolyl, quinolyl,isoquinolyl, isothiazolyl, pyrazolyl, indazolyl, pteridinyl, imidazolyl,triazolyl, tetrazolyl, oxazolyl, isoxazolyl, oxadiazolyl, thiadiazolyl,pyrrolyl, thiazolyl, furyl or thienyl.

The term “cycloalkyl” refers to saturated monocyclic, bicyclic,tricyclic, or other polycyclic hydrocarbon groups. Any atom can besubstituted, e.g., by one or more substituents. A ring carbon serves asthe point of attachment of a cycloalkyl group to another moiety.Cycloalkyl groups can contain fused rings. Fused rings are rings thatshare a common carbon atom. Cycloalkyl moieties can include, e.g.,cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl,adamantyl, and norbornyl (bicycle[2.2.1]heptyl).

The term “aralkyl” refers to an alkyl moiety in which an alkyl hydrogenatom is replaced by an aryl group. One of the carbons of the alkylmoiety serves as the point of attachment of the aralkyl group to anothermoiety. Aralkyl includes groups in which more than one hydrogen atom onan alkyl moiety has been replaced by an aryl group. Any ring or chainatom can be substituted e.g., by one or more substituents. Non-limitingexamples of “aralkyl” include benzyl, 2-phenylethyl, 3-phenylpropyl,benzhydryl (diphenylmethyl), and trityl (triphenylmethyl) groups.

The term “heteroaralkyl” refers to an alkyl moiety in which an alkylhydrogen atom is replaced by a heteroaryl group. One of the carbons ofthe alkyl moiety serves as the point of attachment of the aralkyl groupto another moiety. Heteroaralkyl includes groups in which more than onehydrogen atom on an alkyl moiety has been replaced by a heteroarylgroup. Any ring or chain atom can be substituted e.g., by one or moresubstituents. Heteroaralkyl can include, for example, 2-pyridylethyl.

The term “heterocyclyl” or “heterocyclic”, which are synonymous as usedherein, means a saturated or unsaturated non-aromatic ring containing atleast 5-10 atoms (preferably 5 or 6) and at least one heteroatom(typically 1 to 5 heteroatoms) selected from nitrogen, oxygen or sulfur.The heterocyclyl ring may be monocyclic (with preferably 5 or 6 atoms)or bicyclic (with preferably 9 or 10 atoms). The ring system has 1-4heteroatoms if monocyclic, 1-8 heteroatoms if bicyclic, or 1-10heteroatoms if tricyclic, the heteroatoms selected from O, N, or S (andmono and dioxides thereof, e.g., N→O⁻, S(O), SO₂). The heterocyclylgroups can contain fused rings. Fused rings are rings that share acommon carbon atom. Examples of heterocycle groups include pyrrolidine,piperidine, imidazolidine, pyrazolidine, butyrolactam, valerolactam,imidazolidinone, hydantoin, dioxolane, phthalimide, piperidine,1,4-dioxane, morpholine, thiomorpholine, thiomorpholine-S-oxide,thiomorpholine-S,S-dioxide, piperazine, pyran, pyridone, 3-pyrroline,thiopyran, pyrone, tetrahydrofuran, tetrahydrothiophene, quinuclidineand the like.

The term “ring” means a compound whose atoms are arranged in formulas ina cyclic form. The ring compound can be either carbocyclic orheterocyclic.

The term “alkoxy” refers to an —O-alkyl radical. The term “mercapto”refers to an SH radical. The term “thioalkoxy” refers to an —S-alkylradical. The terms “aryloxy” and “heteroaryloxy” refer to an —O-arylradical and —O-heteroaryl radical, respectively. The terms “thioaryloxy”and “thioheteroaryloxy” refer to an —S-aryl radical and —S-heteroarylradical, respectively.

The terms “aralkoxy” and “heteroaralkoxy” refer to an —O-aralkyl radicaland —O-heteroaralkyl radical, respectively. The terms “thioaralkoxy” and“thioheteroaralkoxy” refer to an —S-aralkyl radical and —S-heteroaralkylradical, respectively. The term “cycloalkoxy” refers to an —O-cycloalkylradical. The terms “cycloalkenyloxy” and “heterocycloalkenyloxy” referto an —O-cycloalkenyl radical and —O-heterocycloalkenyl radical,respectively. The term “heterocyclyloxy” refers to an —O-heterocyclylradical. The term “thiocycloalkoxy” refers to an —S-cycloalkyl radical.The terms “thiocycloalkenyloxy” and “thioheterocycloalkenyloxy” refer toan —S-cycloalkenyl radical and —S-heterocycloalkenyl radical,respectively. The term “thioheterocyclyloxy” refers to an—S-heterocyclyl radical.

The term “cycloalkenyl” refers to partially unsaturated monocyclic,bicyclic, tricyclic, or other polycyclic hydrocarbon groups. A ringcarbon (e.g., saturated or unsaturated) is the point of attachment ofthe cycloalkenyl substituent. Any atom can be substituted e.g., by oneor more substituents. The cycloalkenyl groups can contain fused rings.Fused rings are rings that share a common carbon atom. Cycloalkenylmoieties can include, e.g., cyclohexenyl, cyclohexadienyl, ornorbornenyl.

The term “heterocycloalkenyl” refers to partially unsaturatedmonocyclic, bicyclic, tricyclic, or other polycyclic hydrocarbon groupshaving 1-4 heteroatoms if monocyclic, 1-8 heteroatoms if bicyclic, or1-10 heteroatoms if tricyclic, said heteroatoms selected from O, N, or S(and mono and dioxides thereof, e.g., N→O⁻, S(O), SO₂) (e.g., carbonatoms and 1-4, 1-8, or 1-10 heteroatoms of N, O, or S if monocyclic,bicyclic, or tricyclic, respectively). A ring carbon (e.g., saturated orunsaturated) or heteroatom is the point of attachment of theheterocycloalkenyl substituent. Any atom can be substituted, e.g., byone or more substituents. The heterocycloalkenyl groups can containfused rings. Fused rings are rings that share a common carbon atom.Heterocycloalkenyl groups can include, e.g., tetrahydropyridyl,dihydropyranyl, 4,5-dihydrooxazolyl, 4,5-dihydro-1H-imidazolyl,1,2,5,6-tetrahydro-pyrimidinyl, and 5,6-dihydro-2H-[1,3]oxazinyl.

The term “substituent” refers to a group “substituted” on, e.g., analkyl, cycloalkyl, alkenyl, alkynyl, aralkyl, heteroaralkyl,heterocyclyl, heterocycloalkenyl, cycloalkenyl, aryl, heteroaryl,arylcycloalkyl, heteroarylcycloalkyl, arylcycloalkenyl,heteroarylcycloalkenyl, arylheterocyclyl, heteroarylheterocyclyl,arylheterocycloalkenyl, or heteroarylheterocycloalkenyl group at anyatom of that group. In one aspect, the substituent(s) (e.g., R^(a)) on agroup are independently any one single, or any combination of two ormore of the permissible atoms or groups of atoms delineated for thatsubstituent. In another aspect, a substituent may itself be substitutedwith any one of the above substituents (e.g., R⁶).

In general, and unless otherwise indicated, substituent (radical) prefixnames are derived from the parent hydride by either (i) replacing the“ane” in the parent hydride with the suffixes “yl,” “diyl,” “triyl,”“tetrayl,” etc.; or (ii) replacing the “e” in the parent hydride withthe suffixes “yl,” “diyl,” “triyl,” “tetrayl,” etc. (here the atom(s)with the free valence, when specified, is (are) given numbers as low asis consistent with any established numbering of the parent hydride).Accepted contracted names, e.g., adamantyl, naphthyl, anthryl,phenanthryl, furyl, pyridyl, isoquinolyl, quinolyl, and piperidyl, andtrivial names, e.g., vinyl, allyl, phenyl, and thienyl are also usedherein throughout. Conventional numbering/lettering systems are alsoadhered to for substituent numbering and the nomenclature of fused,bicyclic, tricyclic, polycyclic rings.

In general, when a definition for a particular variable includes bothhydrogen and non-hydrogen (halo, alkyl, aryl, etc.) possibilities, theterm “substituent(s) other than hydrogen” refers collectively to thenon-hydrogen possibilities for that particular variable.

All of the above terms (e.g., “alkyl,” “aryl,” “heteroaryl” etc.), insome embodiments, include both substituted and unsubstituted forms ofthe indicated groups. These groups may be substituted multiple times, aschemically allowed.

The term “composition” as used herein is intended to encompass a productcomprising the specified ingredients in the specified amounts, as wellas any product which results, directly or indirectly, from combinationof the specified ingredients in the specified amounts.

Compositions

A leveling composition comprises a compound of formula (I):

The anion X can be any suitable anion. In some embodiments, X are anionsfrom organic acid, such as acetate, formate, oxalate, or cyanide. Insome embodiments, X is carbonate, bicarbonate, phosphate, sulfate, ornitrate. In some embodiments, X is a halogen anion, such as F³¹ , Cl⁻,Br⁻, or I⁻. In some embodiments, X is Cl⁻, or Br⁻.

R¹ is O, S or N. In some embodiments, R¹ is O.

R² , R³ and R₄ are independently selected from the group consisting ofhydrogen, unsubstituted or substituted alkyl, unsubstituted orsubstituted alkenyl, unsubstituted or substituted alkynyl, unsubstitutedor substituted C₃₋₁₂cycloalkyl, unsubstituted or substituted C₆₋₁₂ aryl,unsubstituted or substituted 3-12 membered heterocyclic, andunsubstituted or substituted 5-12 membered heteroaryl; or R² and R³ maycombine with an atom or atoms to which they are attached to formunsubstituted or substituted C₃₋₁₂cycloalkyl, unsubstituted orsubstituted 3- to 12-membered heterocyclic, unsubstituted or substitutedC₆₋₁₂ aryl, or unsubstituted or substituted 5- to 12- memberedheteroaryl.

In some embodiments, R², R³ and R⁴ are each independently unsubstitutedor substituted alkyl. In some embodiments, R², R³ and R⁴ are eachindependently C₁₋₆alkyl. In some embodiments, R², R³ and R⁴ areindependently selected from the group consisting of methyl, ethyl,propyl, and butyl. In some embodiments, R², R³ and R⁴ are independentlyselected from the group consisting of methyl, ethyl and isopropyl. Inone embodiment, R² is methyl, and R³ and R⁴ are isopropyl. In oneembodiment, R² and R³are ethyl. In one embodiment, R⁴ is benzyl.

Y¹, Y², Y³, Y⁴, Y⁵, Y⁶, Y⁷, and Y⁸ are independently selected for thegroup consisting of hydrogen, halogen, unsubstituted or substitutedalkyl, unsubstituted or substituted alkenyl, unsubstituted orsubstituted alkynyl, unsubstituted or substituted C₃₋₁₂cycloalkyl,unsubstituted or substituted C₆₋₁₂ aryl, unsubstituted or substituted3-12 membered heterocyclic, and unsubstituted or substituted 5-12membered heteroaryl.

In some embodiments, Y¹, Y², Y³, Y⁴, Y⁵, Y⁶, Y⁷, and Y⁸ are eachindependently unsubstituted or substituted alkyl. In some embodiments,R², R³ and R⁴ are each independently C₁₋₃ alkyl. In some embodiments,Y¹, Y², Y³, Y⁴, Y⁵, Y⁶, Y⁷, and Y⁸ are hydrogen. In some embodiments, atleast one of Y¹, Y², Y³, Y⁴, Y⁵, Y⁶, Y⁷, and Y⁸ is halogen.

L is selected from the group consisting of unsubstituted or substitutedalkyl, unsubstituted or substituted C₆₋₁₂ aryl, and unsubstituted orsubstituted 3- to 12-membered heterocyclyl. In some embodiments, L is—(CH₂)_(m)—. m is an Integer. In some embodiments, m is one or two.

In one embodiment, the leveling composition comprises a compound offormula (II):

R¹ is O, S or N. In some embodiments, R¹ is O.

R², R³ and R⁴ are independently selected from the group consisting ofhydrogen, unsubstituted or substituted alkyl, unsubstituted orsubstituted alkenyl, unsubstituted or substituted alkynyl, unsubstitutedor substituted C₃₋₁₂ cycloalkyl, unsubstituted or substituted C₆₋₁₂aryl, unsubstituted or substituted 3-12 membered heterocyclic, andunsubstituted or substituted 5-12 membered heteroaryl; or R² and R³ maycombine with an atom or atoms to which they are attached to formunsubstituted or substituted C₃₋₁₂ cycloalkyl, unsubstituted orsubstituted 3- to 12-membered heterocyclic, unsubstituted or substitutedC₆₋₁₂ aryl, or unsubstituted or substituted 5- to 12- memberedheteroaryl.

In some embodiments, R², R³ and R⁴ are each independently unsubstitutedor substituted alkyl. In some embodiments, R², R³ and R⁴ are eachindependently C₁₋₆alkyl. In some embodiments, R², R³ and R⁴ areindependently selected from the group consisting of methyl, ethyl,propyl, and butyl. In some embodiments, R², R³ and R⁴ are independentlyselected from the group consisting of methyl, ethyl and isopropyl. Inone embodiment, R² is methyl, and R³ and R⁴ are isopropyl. In oneembodiment, R² and R³ are ethyl. In one embodiment, R⁴ is benzyl.

A compound is of formula (III):

R¹ is O, S or N. In some embodiments, R¹ is O.

R², R³ and R⁴ are independently selected from the group consisting ofhydrogen, unsubstituted or substituted alkyl, unsubstituted orsubstituted alkenyl, unsubstituted or substituted alkynyl, unsubstitutedor substituted C₃₋₁₂ cycloalkyl, unsubstituted or substituted C₆₋₁₂aryl, unsubstituted or substituted 3-12 membered heterocyclic, andunsubstituted or substituted 5-12 membered heteroaryl; or R² and R³ maycombine with an atom or atoms to which they are attached to formunsubstituted or substituted C₃₋₁₂ cycloalkyl, unsubstituted orsubstituted 3- to 12-membered heterocyclic, unsubstituted or substitutedC₆₋₁₂ aryl, or unsubstituted or substituted 5- to 12- memberedheteroaryl.

In some embodiments, R², R³ and R⁴ are each independently unsubstitutedor substituted alkyl. In some embodiments, R², R³ and R⁴ are eachindependently C₁₋₆alkyl. In some embodiments, R², R³ and R⁴ areindependently selected from the group consisting of methyl, ethyl,propyl, and butyl. In some embodiments, R², R³ and R⁴ are independentlyselected from the group consisting of methyl, ethyl and isopropyl. Inone embodiment, R² is methyl, and R³ and R⁴ are isopropyl. In oneembodiment, R² and R³are ethyl. In one embodiment, R⁴ is benzyl.

The described leveler is an organic ammonium salt and possess relativelylarge conjugated system like aromatic rings on its side chains. Themolecular weight of these levelers is in the range from ca. 300 to ca.3000.

An exemplary leveler compound is L113, the structure of which is

Another exemplary leveler molecule is L117, the structure of which is

The present invention is directed to the composition of a new class ofeffective leveler additives in metal plating, particularly, in acidcopper plating.

The present invention is also directed to a method of applying the saidcompounds in acid copper plating chemistries to electrodeposit coppertraces and lines (RDLs) and copper pillars with good surface morphologyand good within die uniformity.

In one embodiment, the said leveler in combination with an accelerator,a suppressor, and a VMS, produces copper pillars with different surfacemorphology by simply varying the concentration of the said leveler inthe plating solution.

In yet another embodiment, the said leveler in combination with anaccelerator, a suppressor, and a VMS, produces copper pillars withcompletely flat topography over a wide range of feature sizes (eg,diameters from 10 to 100 microns)

In yet another embodiment, the said leveler in combination with anotherleveler, an accelerator, a suppressor, and a VMS, produces copperpillars with different surface morphologies by varying theconcentrations of the two levelers in the plating solution.

In yet another embodiment, the said leveler in combination with anotherleveler, an accelerator, a suppressor, and a VMS, produces copperpillars with flat topography, good within die uniformity with microbumps(definition: bump diameter <20 microns).

A wide variety of leveler compounds may be prepared from the reaction ofxanthene-9-carboxylate or its derivatives having general structures (Ia)and aryl chlorinate having the general structures of (Ib). Reactions toprepare the leveler compounds may occur according to the conditionsdescribed in U.S. Pat. No. 2,659,732.

The compound has formula (Ia):

R¹, R², and R³ are defined as above.

Another compound has formula (Ib):

R¹, Y¹, Y², Y³, Y⁴, and Y⁵ are defined as above.

In some embodiments, the leveler compound has formula (III), and theleveler may be prepared by selecting reaction conditions, i.e.temperature, concentration, etc., wherein the repeat units of thepolymer comprise one moiety derived from formula (I).

The leveler compound may be added to the electrolytic copper depositionchemistry at a concentration between 0.1 mg/L to 400 mg/L, preferablyfrom about 1 mgL to about 80 mg/L, more preferably from 2 mg/L to about30 mg/L. The levelers are typically prepared by adding other minoringredients (as masking agents, in less than 100 mg/L), and then dilutedwith high purity water. A portion of this leveler solution is then addedto the electrolytic copper plating composition in the concentrationsindicated above. Advantageously, electrolytic copper platingcompositions have been discovered to be tolerant to relatively higherconcentrations of the leveler concentrations of the leveler compounds ofthe present invention compared to conventional leveler compounds. Thatis, an electrolytic copper plating composition may be tolerant to higherconcentrations of the leveler compounds of the presentation inventionwithout negatively impacting the copper deposition quality, i.e.,surface morphology and deposition rate.

The electrolytic copper deposition chemistry of the present inventionadditionally comprises a source of copper ions, chloride ions, an acid,an accelerator, and a suppressor. The composition may comprise othermaterials that have other deposit properties, such as wetters, grainrefiners, secondary brighteners, carriers, levelers and the like. Inembodiments wherein an alloy is to be deposited, the electrolytic copperdeposition chemistry further comprises a source of metal ions of thealloying metal that may be selected from among a source of tin ions, asource of silver ions, a source of zinc ions, a source of manganeseions, a source of zirconium ions, a source of bismuth ions, or a sourceof transition or refractory metal ions.

In embodiments wherein the metal or metals to be electrolyticallydeposited does not include copper, the deposition chemistry of thepresent invention additionally comprises a source of ions of the metalor metals to be deposited, such as a source of tin ions, a source ofsilver ions, a source of zinc ions, a source of manganese ions, a sourceof zirconium ions, a source of bismuth ions, or a source of transitionor refractory metal ions, an acid, an accelerator, and a suppressor.

The accelerator and suppressor work together in a manner thatadvantageously enhances plating performance in conformal plating andsurface appearance. Conformal plating is characterized by a deposit ofequal thickness at all points of a feature (therefore flat). Conformalplating results from relatively equal copper deposition suppressionacross the entire feature surface and across the entire die. This couldonly be achieved with a superior leveling agent such as the ones in thepresent invention.

The accelerator may include an organic sulfur compound. Organic sulfurcompounds currently preferred by the applicants are water solubleorganic divalent sulfur compounds. In one preferred embodiment, theorganic sulfur compound has the following general formula (IV):

Wherein X is O or S, preferably S;

n is 1 to 6;

M is hydrogen, alkali metal, or ammonium as needed to satisfy thevalence;

R₁ is an alkylene or cyclic alkylene group of 1 to 8 carbon atoms, anaromatic hydrocarbon of 6 to 12 carbon atoms; and

R₂ is selected from the group of MO₃SR₁ wherein M and R₁ are asdescribed above.

A preferred organic sulfur compound of formula (IV) has the followinggeneral formula (V), wherein M is a counter ion possessing sufficientpositive charge to balance the negative charge on the oxygen atoms. Mmay be, for example, protons, alkali metal ions such as sodium andpotassium, or another charge balancing cation such as ammonium or aquaternary amine.

One example of the organic sulfur compound of formula (V) is the sodiumsalt of 3,3′-dithiobis(1-propane-sulfonate), which has the followingformula (VI):

An especially preferred example of the organic sulfur compound offormula (VII) is 3,3′-dithiobis(1-propane-sulfonic acid), which has thefollowing formula (VII):

The organic sulfur compound may be added in concentration between about1 mg/L to about 50 mg/L, (ppm), preferably between about 3 mg/L to 30mg/L, such as between about 15 mg/L and 25 mg/L. In a preferredembodiment, the organic sulfur compound is3,3′dithiobis(1-propanesulfonic acid) added in a concentration of about20 mg/L

Suppressors typically comprise a polyether group covalently bonded to abase moiety. One class of applicable suppressors comprises a polymergroup covalently bonded to an alcohol initiating moiety. With regard tosuppressors comprising a polyether group covalently bonded to aninitiating moiety comprising an ether group derived from an alcoholinitiating moiety, the suppressor comprises at least two distinct etherfunctional groups; (1) an ether group derived from a reaction betweenalcohol and a random glycol unit or the polyether chain, and (2) ethergroups derived from reactions between random glycol units within thepolyether chain.

In those embodiments where the polyether chain comprises an initiatingmoiety comprising ether group derived from an alcohol, suitable alcoholsinclude substituted or unsubstituted acyclic alcohols and substituted orunsubstituted cyclic alcohols. The alcohol comprises at least onehydroxyl group, and thus can be an alcohol or a polyol, the polyolcomprising two or more hydroxyl groups such as between about twohydroxyl groups to about six hydroxyl groups. Acyclic alcohols comprisea substituted or unsubstituted alkyl, preferably a short chainhydrocarbon having between one and about twelve carbons, more preferablybetween about four and about ten carbons, which may be branched orstraight chained. Exemplary acyclic alcohols include n-butanol,iso-butanol, tert-butanol, pentanol, neopentanol, tert-army alcohol,ethylene glycol, 1,2-butanediol, 1,3-butandio 1,1,4-butandiol, andglycercol, among others. Cycloalkyl groups typically have a 5- to7-carbon ring, although bicylic, tricylic, and higher multi-cyclic alkylgroups are applicable.

The polyether comprises a chain of random glycol units wherein the chainof random glycol units can be formed by the polymerization of epoxidemonomers. Preferably, the polyether comprises a chain of random glycolunits formed by the polymerization of both ethylene oxide monomer andpropylene oxide monomer. The ratio of ethylene oxide (EO) glycol unitsand propylene oxide (PO) glycol units in the polyether can be betweenabout 1:9 to about 9:1. In some embodiments, the ratio is betweenabout1:3 to about 3:1, such as about 1:1. The random polyether cancomprise up to about 800 EO glycol units and up to about 250 PO glycolunits. In a preferred embodiment, the random polyether comprises betweenabout 20 and about 25 EO glycol units and between about 15 and about 20PO glycol units. The molecule weight of the random polyether can be aslow as 500 g/mole and as high as about 50,000 g/mole, preferably betweenabout 1000 g/mole to 20,000 g/mole, and more preferably between 1000g/mole to 10,000 g/mole.

An exemplary suppressor compound comprising a polyether group covalentlybonded to a moiety derived from an alcohol is shown in formula (VII)Formula VIII is a suppressor comprising a PO/EO random copolymercovalently bonded to a moiety derived from n-butanol having thestructure

—(CH₂)₃—(OC₃H₆)_(m)/(OC₂H₄)_(n)—  (VIII)

Wherein n can be between 1 and about 200 and m can be between 1 andabout 200. The number ratio of EO:PO units is such that the suppressorcompound preferably comprises between about 45% and about 55% by weightEO units and between about 55% and 45% by weight PO units, the EO and POunits arranged randomly in the polyether chain. The molecular weight ofthe random PO/EO copolymer can be between about 2000 g/mole to about20,000 g/mole, and preferably between about 1500 g/mole to about 4500g/mole

An exemplary suppressor compound having the formula VIII is availablefrom Aladdin Chemistry Co. Ltd., under the trade designation Polyethylene glycol.

Wide variety of electrolytic copper deposition chemistries arepotentially applicable. The electrolytic baths include acid baths andalkaline baths, exemplary electrolytic copper plating baths includecopper fluoroborate, copper pyrophosphate, copper cyanide, copperphosphate, copper sulfate, and other copper metal complexes such ascopper methane sulfonate and copper hydroxylethylsulonate. Preferredcopper sources include copper sulfate in sulfuric acid solution andcopper methane sulfonate in methane sulfonic acid solution.

In embodiments wherein the copper source is copper sulfate and acid issulfuric acid, the concentration of copper ion and acid may vary overwide limits; for example, from about 4 to 70 g/L copper and from about 2to about 225 g/L sulfuric acid. In this regard the compounds of theinvention are suitable for use in distinct acid/copper concentrationranges, such as high acid/low copper systems, in low acid/high coppersystems, and mid acid/high copper systems. In high acid/low coppersystems, the copper ion concentration can be on the order of 4 g/L to onthe order of 30 g/L; and the acid concentration may be sulfuric acid inan amount greater than about 100 g/L up to 225 g/L. In an exemplary highacid low copper system, the copper ion concentration is about 17 g/L,where the sulfuric acid concentration is about 180 g/L. In some lowacid/high copper systems, the copper ion concentration can be between 35g/L to about 65 g/L, such as between 38 g/L and about 50 g/L. 35 g/Lcopper ion corresponds to about 140 g/L CuSO₄.5H₂O, copper sulfatepentahydrate. In some low acid high copper systems, the copper ionconcentration can be between 30 to 60 g/L, such as between 40 g/L toabout 50 g/L. The acid concentration in these systems is preferably lessthan about 100 g/L.

In other embodiments, the copper source is copper methanesulfonate andthe acid is methanesulfonic acid. The use of copper mathanesulfonate asthe copper source allows for greater concentrations of copper ions inthe electrolytic copper deposition chemistries in comparison to othercopper ion sources. Accordingly, the source of copper ion may be addedto achieve copper ion concentrations greater than about 80 g/L, greaterthan about 90 g/L, or even greater than about 100 g/L, such as, forexample about 110 g/L. Preferably, the copper methanesulfonate is addedto achieve a copper ion concentration between about 30 g/L to about 100g/L, such as between about 40 g/L and about 60 g/L. High copperconcentrations enabled by the used of copper methanesulfonate is thoughtto be one method for alleviating the mass transfer problem, i.e., localdepletion of copper ions particularly at the bottom of deep features.High copper concentrations in the bulk solution contribute to a stepcopper concentration gradient that enhances diffusion of copper into thefeatures.

When copper methane sulfonate is used, it is preferred to use methanesulfonic acid for acid pH adjustment. This avoids the introduction ofunnecessary anions into the electrolytic deposition chemistry. Whenmethane sulfonic acid is added, its concentration may be between about 1ml/L to about 400 ml/L.

Chloride ion may also be used in the bath at a level up to about 200mg/L (about 200 ppm), preferably from about 10 mg/L to about 90 mg/L(about 10 to 90 ppm), such as about 50 mg/L (about 50 ppm). Chloride ionis added in these concentration ranges to enhance the function of otherbath additives. In particular, it has been discovered that the additionof chloride ion enhances the effectiveness of a leveler. Chloride ionsare added using HCl.

A source of alloying metal ions may be added to the composition to platea copper alloy. Sources of alloying metal ions include a source of tinions, a source of silver ions, a source of zinc ions, a source ofmanganese ions, a source of zirconium ions, a source of bismuth ions, ora source of transition or refractory metal ions. Typically, the sourcesof these alloying metal ions many be the same as the source of thecopper ions. That is, if a copper sulfate is used as the copper source,it is preferred to use tin sulfate and zinc sulfate as the alloyingmetal ion sources. Alternatively, if copper methane sulfonate is used,the sources of tin ions and zinc ions are preferably methanesulfonatesalts of these ions. These are typically added in concentrations from0.05 to about 25 g/L. The concentration may vary depending upon thedesired alloy metal content in the deposited copper alloy.

A large variety of additives may typically be used in the bath toprovide desired surface finishes and metallurgies for the plated coppermetal. Usually more than one additive is used to achieve desiredfunctions. At least two or three additives are generally used toinitiate good copper deposition as well as to produce desirable surfacemorphology with good conformal plating characteristics. Additionaladditives (usually organic additives) include wetter, grain refiners andsecondary brighteners and polarizers for the suppression of dendriticgrowth, improved uniformity and defect reduction.

Plating equipment for plating semiconductor substrates is well known andis described in, for example, Haydu et al. U.S. Pat. No. 6,024,856.Plating equipment comprises an electrolytic plating tank which holdscopper electrolytic solution and which is made of a suitable materialsuch as plastic or other material inert to the electrolytic platingsolution. The tank may be cylindrical, especially for wafer plating. Acathode is horizontally disposed at the upper part of the tank and maybe any type of substrate such as a silicon wafer having openings such aslines and vias. The wafer substrate is typically coated first withbarrier layer, which may be titanium nitride, tantalum, tantalumnitride, or ruthenium to inhibit copper diffusion, and next with a seedlayer of copper or other metal to initiate copper electrodeposition. Acopper seed layer may be applied by chemical vapor deposition (CVD),physical vapor deposition (PVD), or the like. An anode is alsopreferably circular for wafer plating and is horizontally disposed atthe lower part of tank forming a space between the anode and thecathode. The anode is typically a soluble anode such as copper metal.

The bath additives can be used in combination with membrane technologybeing developed by various plating tool manufacturers. In this system,the anode may be isolated from the organic bath additives by a membrane.The purpose of the separation of the anode and the organic bathadditives is to minimize the oxidation of the organic bath additives onthe anode surface.

The cathode substrate and anode are electrically connected by wiringand, respectively, to a rectifier (power supply). The cathode substratefor direct or pulse current has a net negative charge so that copperions in the solution are reduced at the cathode substrate forming platedcopper metal on the cathode surface. An oxidation reaction takes placeat the anode. The cathode and anode may be horizontally or verticallydisposed in the tank.

During operation of the electrolytic plating system, a pulse current,direct current, reverse periodic current, or other suitable current maybe employed. The temperature of the electrolytic solution may bemaintained using a heater/cooler whereby electrolytic solution isremoved from the holding tank and flows through the heater/cooler and itis recycled to the holding tank.

Electrodeposition conditions such as applied voltage, current density,solution temperature, and flow condition are essentially the same asthose in conventional electrolytic copper plating methods. For example,the bath temperature is typically about room temperatures such as about20 to 27° C., but may be at elevated temperatures up to about 40° C., orhigher. The electrical current density is typically from about 0.2 A/dm²to about 6 A/dm², but may also be up to about 20 A/dm², such as about 10A/dm². It is preferred to use an anode to cathode ratio of 1:1, but thismay also vary widely from about 1:4 to about 4:1. The process also usesmixing in the electrolytic plating tank which may be supplied byagitation or preferably by the circulating flow of recycle electrolyticsolution through the tank.

Copper deposited from the electrolytic deposition chemistry of thepresent invention comprising the above described leveler compounds is ofhigh purity and density, is of high smoothness and flat surfacetopography.

Having described the invention in detail, it will be apparent thatmodifications and variations are possible without departing from thescope of the invention defined in the appended claims.

EXAMPLES

The following non-limiting examples are provided to further illustratethe present invention. While the leveler of present invention can beused in electroplating of metals such as copper, tin, nickel, zinc,silver, gold, palladium, platinum, and iridium, only electrolytic copperplating chemistries are described below.

Example 1 (FIG. 4) Electrolytic Copper Deposition Chemistry of theInvention

An electrolytic copper plating composition of the invention was preparedhaving the following components and concentrations

-   -   a. Copper ion from copper sulfate (50 g/L, Cu²⁺)    -   b. Sulfuric acid (100 g/L)    -   c. Chloride ion (70 ppm)    -   d. L113 (30 ppm)

The electrolytic copper deposition chemistry was prepared according tothe instructions of Table I. Plating conditions are summarized in TableII

TABLE I Bath composition Components Concentration Unit Preparation VMSCuSO4•5H2O 200 g/L Calculated amount of CuSO4•5H2O is dissolved with(500 ml) H2SO4 100 g/L double distilled water, calculated amount of Cl⁻80 ppm H2SO4 and HCl was then added slowly, the solution is thenfiltered and diluted to 1 L. 500 mL of the prepared solution wastransferred to a beaker for subsequent use. Additives Suppressor 1000ppm The additives in solid form are dissolved with double Levelercalculated ppm- distilled water and diluted to 50 ml, calculated amountof Accelerator 10 ppm suppressor, leveler, and accelerator products arethen added to the plating bath and stirred at 500 rpm for 20~30 min.

TABLE II Hull Cell Plating Conditions Target bump thickness CurrentPlating duration Agitation (um) (A) (min) (rpm) 5 3 2 Air agitation

Example 2 (FIG. 5) Electrolytic Copper Deposition Chemistry of theInvention

An electrolytic copper plating composition of the invention was preparedhaving the following components and concentrations

-   -   a. Copper ion from copper sulfate (50 g/L, Cu²⁺)    -   b. Sulfuric acid (100 g/L)    -   c. Chloride ion (70 ppm)    -   d. L113 (30 ppm)    -   e. S24 (1000 ppm)

The electrolytic copper deposition chemistry was prepared according tothe instructions of Table I. Plating conditions are summarized in TableII

Example 3 (FIG. 6) Electrolytic Copper Deposition Chemistry of theInvention

An electrolytic copper plating composition of the invention was preparedhaving the following components and concentrations

-   -   a. Copper ion from copper sulfate (50 g/L, Cu²⁺)    -   b. Sulfuric acid (100 g/L)    -   c. Chloride ion (70 ppm)    -   d. L113 (30 ppm)    -   e. S24 (1000 ppm)    -   f. A28 (10 ppm)

The electrolytic copper deposition chemistry was prepared according tothe instructions of Table I. Plating conditions are summarized in TableII

Example 4 (FIG. 7) Comparative Electrolytic Copper Deposition Chemistry

An electrolytic copper plating composition of a conventional system wasprepared having the following components and concentrations

-   -   a. Copper ion from copper sulfate (50 g/L, Cu²⁺)    -   b. Sulfuric acid (100 g/L)    -   c. Chloride ion (70 ppm)    -   d. L26 (conventional leveler, 30 ppm)    -   e. S24 (1000 ppm)    -   f. A28 (10 ppm)

The electrolytic copper deposition chemistry was prepared according tothe instructions of Table I. Plating conditions are summarized in TableII.

Example 5 (FIGS. 8,11,14,17,20, and 24) Electrolytic Copper DepositionChemistry of the Prior Art

An electrolytic copper plating composition of the invention was preparedhaving the following components and concentrations

-   -   a. Copper ion from copper sulfate (50 g/L, Cu²⁺)    -   b. Sulfuric acid (100 g/L)    -   c. Chloride ion (70 ppm)    -   d. L26 (30 ppm)    -   e. S24 (1000 ppm)    -   f. A28 (10 ppm)

The electrolytic copper deposition chemistry was prepared according tothe instructions of Table I. Plating conditions are summarized in TableIII.

TABLE III Wafer Plating Conditions Plating Target bump Current Agitationarea height density Current Plating duration speed (cm2) (um) (ASD) (mA)(min) (rpm) 0.21 50 10 21 22 110

Example 6 (FIGS. 9,12,15,18, 21, and 25) Electrolytic Copper DepositionChemistry of the Invention

An electrolytic copper plating composition of the invention was preparedhaving the following components and concentrations

-   -   a. Copper ion from copper sulfate (50 g/L, Cu2+)    -   b. Sulfuric acid (100 g/L)    -   c. Chloride ion (70 ppm)    -   d. L113 (30 ppm)    -   e. S24 (1000 ppm)    -   f. A28 (10 ppm)        The electrolytic copper deposition chemistry was prepared        according to the instructions of Table I. Plating conditions are        summarized in Table III.

Example 7 (Figures 10,13,16,19,22, and 26) Electrolytic CopperDeposition Chemistry of the Invention (Preferred for Microbumps)

An electrolytic copper plating composition of the invention was preparedhaving the following components and concentrations

-   -   a. Copper ion from copper sulfate (50 g/L, Cu²⁺)    -   b. Sulfuric acid (100 g/L)    -   c. Chloride ion (70 ppm)    -   d. L117 (30 ppm)    -   e. S24 (1000 ppm)    -   f. A28 (10 ppm)

The electrolytic copper deposition chemistry was prepared according tothe instructions of Table I. Plating conditions are summarized in TableIII

Example 8 (FIGS. 23 and 27) Electrolytic Copper Deposition Chemistry ofthe Invention (Preferred)

An electrolytic copper plating composition of the invention was preparedhaving the following components and concentrations

-   -   a. Copper ion from copper sulfate (50 g/L, Cu²⁺)    -   b. Sulfuric acid (100 g/L)    -   c. Chloride ion (70 ppm)    -   d. L117 (9 ppm)+L26 (14 ppm)    -   e. S24 (1000 ppm)    -   f. A28 (10 ppm)

The electrolytic copper deposition chemistry was prepared according tothe instructions of Table I. Plating conditions are summarized in TableIII.

What is claimed is:
 1. A leveling composition for electrodeposition ofmetals, comprising a compound of formula (I):

wherein X is or Cl⁻, or Br⁻; R¹ is O, S or N; R², R³ and R⁴ areindependently selected from the group consisting of hydrogen,unsubstituted or substituted alkyl, unsubstituted or substitutedalkenyl, unsubstituted or substituted alkynyl, unsubstituted orsubstituted C₃₋₁₂ cycloalkyl, unsubstituted or substituted C₆₋₁₂ aryl,unsubstituted or substituted 3-12 membered heterocyclic, andunsubstituted or substituted 5-12 membered heteroaryl; or R² and R³ maycombine with an atom or atoms to which they are attached to formunsubstituted or substituted C₃₋₁₂ cycloalkyl, unsubstituted orsubstituted 3- to 12-membered heterocyclic, unsubstituted or substitutedC₆₋₁₂ aryl, or unsubstituted or substituted 5- to 12- memberedheteroaryl; Y¹, Y², Y³, Y⁴, Y⁵, Y⁶, Y⁷, and Y⁸ are independentlyselected from the group consisting of hydrogen, halogen, unsubstitutedor substituted alkyl, unsubstituted or substituted alkenyl,unsubstituted or substituted alkynyl, unsubstituted or substitutedC₃₋₁₂cycloalkyl, unsubstituted or substituted C₆₋₁₂ aryl, unsubstitutedor substituted 3-12 membered heterocyclic, and unsubstituted orsubstituted 5-12 membered heteroaryl; and L is selected from the groupconsisting of unsubstituted or substituted alkyl, unsubstituted orsubstituted C₆₋₁₂ aryl, and unsubstituted or substituted 3- to12-membered heterocyclyl.
 2. The leveling composition of claim 1,wherein R¹ is O.
 3. The leveling composition of claim 1, wherein are Y¹,Y², Y³, Y⁴, Y⁵, Y⁶, Y⁷, and Y⁸ are hydrogen.
 4. The leveling compositionof claim 1, wherein R², R³ and R⁴ are each independently C₁₋₆alkyl. 5.The leveling composition of claim 1, wherein R² is methyl, and R³ and R⁴are isopropyl.
 6. The leveling composition of claim 1, wherein R² and R³are ethyl, and R⁴ is benzyl. 7 The leveling composition of claim 1,comprising a compound of formula (II):

wherein X is Cl⁻, or Br⁻; R¹ is O, S or N; and R², R³ and R⁴ areindependently selected from the group consisting of hydrogen,unsubstituted or substituted alkyl, unsubstituted or substitutedalkenyl, unsubstituted or substituted alkynyl, unsubstituted orsubstituted C₃₋₁₂cycloalkyl, unsubstituted or substituted C₆₋₁₂ aryl,unsubstituted or substituted 3-12 membered heterocyclic, andunsubstituted or substituted 5-12 membered heteroaryl; or R² and R³ maycombine with an atom or atoms to which they are attached to formunsubstituted or substituted C₃₋₁₂cycloalkyl, unsubstituted orsubstituted 3- to 12-membered heterocyclic, unsubstituted or substitutedC₆₋₁₂ aryl, or unsubstituted or substituted 5- to 12- memberedheteroaryl.
 8. The leveling composition of claim 7, wherein R¹ is O. 9.The leveling composition of claim 7, wherein R², R³ and R⁴ are eachindependently C₁₋₆alkyl.
 10. A leveling composition forelectrodeposition of metals, comprising a compound of formula (III):

wherein X is C⁻, or Br⁻; R¹ is O , S or N; R², R³ and R⁴ areindependently selected from the group consisting of hydrogen,unsubstituted or substituted alkyl, unsubstituted or substitutedalkenyl, unsubstituted or substituted alkynyl, unsubstituted orsubstituted C₃₋₁₂cycloalkyl, unsubstituted or substituted C₆₋₁₂ aryl,unsubstituted or substituted 3-12 membered heterocyclic, andunsubstituted or substituted 5-12 membered heteroaryl; or R² and R³ maycombine with an atom or atoms to which they are attached to formunsubstituted or substituted C₃₋₁₂cycloalkyl, unsubstituted orsubstituted 3- to 12-membered heterocyclic, unsubstituted or substitutedC₆₋₁₂ aryl, or unsubstituted or substituted 5- to 12- memberedheteroaryl; and n is 2 to
 100. 11. The leveling composition of claim 10,wherein R¹ is O.
 12. The leveling composition of claim 1, furthercomprising an accelerator, and a suppressor.
 13. The levelingcomposition of claim 1, comprising the compound of formula:


14. The composition of claim 12, wherein the accelerator is of formula:(IV)

Wherein X is O or S; n is 1 to 6; M is hydrogen, alkali metal, orammonium; R¹ is an alkylene or cyclic alkylene group of 1 to 8 carbonatoms; an aromatic hydrocarbon of 6 to 12 carbon atoms; and R² isselected from the group of MO₃SR¹, wherein M and R¹ are as describedabove.
 15. The composition of claim 14, wherein X in formula (III) is S.16. The composition of claim 12, wherein the suppressor is of formula(VIII)H₃C—(CH₂)₃—(OC₃H₆)_(m)/(OC₂H₄)_(n)—  (VIII) Wherein n is between 1 andabout 200 and m is between 1 and about
 200. 17. A method for a metalonto a substrate, comprising: contacting a substrate with anelectrolytic metal deposition composition comprising a source of metalions, and a leveler composition, wherein the leveler compositioncomprises the compound of formula (I):

wherein X is Cl⁻, or Br⁻; R¹ is O, S or N; R², R³ and R⁴ areindependently selected from the group consisting of hydrogen,unsubstituted or substituted alkyl, unsubstituted or substitutedalkenyl, unsubstituted or substituted alkynyl, unsubstituted orsubstituted C₃₋₁₂cycloalkyl, unsubstituted or substituted C₆₋₁₂ aryl,unsubstituted or substituted 3-12 membered heterocyclic, andunsubstituted or substituted 5-12 membered heteroaryl; or R² and R³ maycombine with an atom or atoms to which they are attached to formunsubstituted or substituted C₃₋₁₂cycloalkyl, unsubstituted orsubstituted 3- to 12-membered heterocyclic, unsubstituted or substitutedC₆₋₁₂ aryl, or unsubstituted or substituted 5- to 12-memberedheteroaryl; Y¹, Y², Y³, Y⁴, Y⁵, Y⁶, Y⁷, and Y⁸ are independentlyselected from the group consisting of hydrogen, halogen, unsubstitutedor substituted alkyl, unsubstituted or substituted alkenyl,unsubstituted or substituted alkynyl, unsubstituted or substitutedC₃₋₁₂cycloalkyl, unsubstituted or substituted C₆₋₁₂ aryl, unsubstitutedor substituted 3-12 membered heterocyclic, and unsubstituted orsubstituted 5-12 membered heteroaryl; and L is selected from the groupconsisting of unsubstituted or substituted alkyl, unsubstituted orsubstituted C₆₋₁₂ aryl, and unsubstituted or substituted 3- to12-membered heterocyclyl; and applying an electrical current to theelectrolytic deposition composition to deposit a metal onto thesubstrate.
 18. The method of claims 17, wherein the electrolytic metaldeposition composition further comprises a suppressor compoundcomprising the formula (VIII).
 19. The method of claims 17, wherein theelectrolytic metal deposition composition further comprises anaccelerator of formula (IV).
 20. The method of claim 17, wherein themetal is a copper alloy.
 21. The method of claim 17, wherein the metalsbeing electrolytically deposited are copper and copper alloy.
 22. Themethod of claim 17, wherein copper sulfate is used as the metal source.23. The method of claim 22, further comprising using sulfuric acid. 24.The method of claim 17, wherein copper methanesulfonate is used as themetal source, and methane sulfonic acid is used.